- STRUCTURES IN SOLUTION OF ADDUCTS OF 2,8-DIOXA-5-AZA-1-PHOSPHABICYCLOOCTANE AND SUBSTITUTED BENZILS
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Adducts of 2,8-dioxa-5-aza-1-phosphabicyclooctane and p,p'-dimethylbenzil, p-methoxy-p'-fluorobenzil, p-fluorobenzil, p,p'-difluorobenzil, p-nitrobenzil and p,p'-dinitrobenzil have been prepared.Although these materials could not be isolated in pure form because of rapid decomposition, the 31P and other NMR spectral data indicate that all of these materials are pentacoordinate in solution.The NMR data also indicate that all of these adducts undergo rapid intramolecular ligand reorganosation at room temperature.Variable temperature NMR measurements indicate that these rearrangements can be slowed and that they all have virtually the same activation energies, ΔG(excit.) 11.4-11.9 kcal/mole.The barrier to ligand reorganization is associated with the 5-membered dioxa containing ring adopting a diequatorial disposition.These results are discussed and compared to other systems.
- Denney, Donald B.,Denney, Dorothy Z.,Pastor, Stephen D.
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p. 191 - 198
(2007/10/02)
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